CN109554024A

CN109554024A - Ink group and recording method

Info

Publication number: CN109554024A
Application number: CN201811118524.5A
Authority: CN
Inventors: 奥田平; 奥田一平; 阿左美由子
Original assignee: Seiko Epson Corp
Current assignee: Seiko Epson Corp
Priority date: 2017-09-27
Filing date: 2018-09-25
Publication date: 2019-04-02
Anticipated expiration: 2038-09-25
Also published as: US10723903B2; EP3461866A1; US20190092958A1; CN109554024B; JP2019059872A; JP7017051B2; EP3461866B1

Abstract

It provides in the recording method using deep or light ink, the ink group and recording method of the reliability of erasibility and resistance to blocking can be taken into account.Ink group of the invention is characterized in that, is adhered to together with the reaction solution that the ingredient reaction with printing ink composition is aggregated to recording medium, have: the first printing ink composition, it includes color material, fixing resin and resin dissolubility solvents；And second printing ink composition, it includes color materials, it is fixed resin and resin dissolubility solvent, with first printing ink composition identical colour system ink each other, wherein, according to quality criteria, the content of the color material of second printing ink composition is fewer than the content of the color material of first printing ink composition, according to quality criteria, the content of the fixing resin of second printing ink composition is more than the content of the fixing resin of first printing ink composition, according to quality criteria, the content of the resin dissolubility solvent of second printing ink composition is more than the content of the resin dissolubility solvent of first printing ink composition.

Description

Ink group and recording method

Technical field

The present invention relates to a kind of ink group and recording methods.

Background technique

Small ink drop is sprayed it has been known that there is the nozzle of the ink gun from ink-jet recording apparatus, on the recording medium record figure The ink jet recording method of picture is studying signature print field, the use in label printing field.Also, relative to ink The recording medium (for example, art paper, coating paper) of low absorption or the recording medium (for example, plastic foil) of ink nonabsorbable into In the case where the record of row image, as ink, the viewpoints such as safety in terms of earth environment and to human body are being ground Aqueous inkjet ink composition is studied carefully (hereinafter, also referred to as " aqueous ink " or " ink ".) use.

For using the record of aqueous inkjet ink composition, there are following technologies, i.e., to obtain ash with higher For the purpose of the image of the high-quality of degree property, by the way that the identical colour system ink containing the ingredient for possessing resin isoreactivity is applied in combination Dense ink and light ink (hereinafter, the two is also referred to as " deep or light ink ".), to inhibit color difference, reduce the graininess of image quality Technology (for example, referring to patent document 1).

Citation

Patent document

Patent document 1: Japanese patent application discloses 2004-338259 bulletin.

Summary of the invention

However, using deep or light ink, for the purpose of the ejection stability of raising and head to obtain image quality And when using reaction solution, occupying region especially with the low of light ink, the ingredient of ink is unable to fully react sometimes, image quality Formation becomes difficult, erasibility decline.

Therefore, a kind of at least part by solving in above-mentioned project etc. is provided according to several aspects of the present invention, To which ink group and the record side of the reliability of erasibility and resistance to blocking can be taken into account in the recording method using deep or light ink Method.

The present invention be in order to solve above-mentioned problem at least part and complete, and can as mode below or Application examples is realized.

[application examples 1]

The one side of ink group of the invention, which is characterized in that react and be aggregated anti-with the ingredient with printing ink composition Answer liquid to adhere to together to recording medium, above-mentioned ink group has: the first printing ink composition, it includes color material, fixing resin and trees Rouge dissolubility solvent；And second printing ink composition, it includes color material, fixing resin and resin dissolubility solvent, the second ink groups Close object and above-mentioned first printing ink composition identical colour system ink each other, according to quality criteria, the color of above-mentioned second printing ink composition The content of material is fewer than the content of the color material of above-mentioned first printing ink composition, according to quality criteria, above-mentioned second printing ink composition The content for being fixed resin is more than the content of the fixing resin of above-mentioned first printing ink composition, according to quality criteria, above-mentioned second oil The content of the resin dissolubility solvent of ink composition is more than the content of the resin dissolubility solvent of above-mentioned first printing ink composition.

Fixing tree according to above application examples, by the content of color material less than the second printing ink composition of the first printing ink composition The content of rouge is set as more than the first printing ink composition, and the content of the resin dissolubility solvent of dissolving resin on the recording medium More than the first printing ink composition, thus, it is possible to improve the low erasibility for occupying region using the second printing ink composition.In addition, logical It crosses the temperature using reaction solution, when recording without improving and is also capable of forming image quality, therefore can ensure the ejection stability of head, In recording method using deep or light ink, it is capable of providing the ink group for the reliability for taking into account erasibility and resistance to blocking.

[application examples 2]

In above application examples, the fixing resin that above-mentioned second printing ink composition is included includes: in the environment of 25 DEG C, When 0.3M magnesium sulfate solution and resin liquid being stirred 1 minute with the mass ratio of 1:1, tree of the variation less than 5 times of average grain diameter Rouge, above-mentioned resin liquid are to be scattered in 1 mass % of resin obtained by water.

According to above application examples, fixing resin contained by the second printing ink composition is, in the environment of 25 DEG C, with 1:1's Mass ratio is averaged when stirring 0.3M magnesium sulfate solution and the resin liquid as obtained by 1 mass % of dispersion resin in water 1 minute Reactivity lower resin of the variation of partial size less than 5 times, thus reacted with reaction solution and while forming image be capable of forming it is flat Sliding film, further increases erasibility.Further, since by be fixed after color material first precipitates (reaction) resin covering in a manner of at Film, therefore this is advantageous in erasibility.

[application examples 3]

In above application examples, the content and above-mentioned first printing ink composition of the fixing resin of above-mentioned second printing ink composition Fixing resin content compared to can more than enough 0.5 mass % or more, 5 mass % or less.

According to above application examples, the fixing tree of the content of the fixing resin of the second printing ink composition than the first printing ink composition The content of rouge contains 0.5 mass % or more, 5 mass % hereinafter, thus further increasing erasibility more.

[application examples 4]

In above application examples, the content and above-mentioned first ink combination of the resin dissolubility solvent of the second printing ink composition The content of the resin dissolubility solvent of object 0.5 mass % or more 10 mass % or less more than enough compared to energy.

According to above application examples, the content of the resin dissolubility solvent of the second printing ink composition is than the first printing ink composition The content of resin dissolubility solvent contains 0.5 mass % or more, 10 mass % hereinafter, thus further increasing erasibility more.

[application examples 5]

The content of the resin dissolubility solvent of above-mentioned second printing ink composition can be set as 20 mass % or less.

According to above application examples, the content of the resin dissolubility solvent of the second printing ink composition be 20 mass % hereinafter, by This further increases the reliability of resistance to blocking.

[application examples 6]

In above application examples, the normal boiling point of above-mentioned first printing ink composition and above-mentioned second printing ink composition is more than The content of the organic solvent of 280 DEG C of sub- alkane polyol system can be respectively smaller than 1 mass %.

According to above application examples, the normal boiling point of the first printing ink composition and the second printing ink composition is more than 280 DEG C of Asia The content of the organic solvent of alkane polyol system is respectively smaller than 1 mass %, thus further increases erasibility.

[application examples 7]

In above application examples, the resin dissolubility solvent and fixing resin that above-mentioned second printing ink composition is included can Difference comprising SP value the resin dissolubility solvent within 5 and fixing resin each other.

According to above application examples, the resin dissolubility solvent and fixing resin that the second printing ink composition is included include SP value Difference the resin dissolubility solvent within 5 and fixing resin each other, it is smooth at membranization thus, it is possible to further realize, further Improve erasibility.

[application examples 8]

The one side of recording method of the invention uses the ink group above-mentioned to any of application examples 7 example of application examples 1 It carries out, above-mentioned recording method can have: the process for adhering to above-mentioned reaction solution to recording medium；Make above-mentioned first ink combination The process that object adheres to recording medium；And the process for adhering to above-mentioned second printing ink composition to recording medium.

According to above application examples, the content of color material is less than to the fixing resin of first the second printing ink composition of printing ink composition Content be set as more than the first printing ink composition, and the content of the resin dissolubility solvent of dissolving resin is also more than in recording medium First printing ink composition, thus, it is possible to improve the low erasibility for occupying region using the second printing ink composition.In addition, by making With reaction solution, temperature when being recorded without improving and be capable of forming image quality, therefore can ensure the ejection stability of head, use In the recording method of deep or light ink, it is capable of providing the recording method for taking into account the reliability of erasibility and resistance to blocking.

[application examples 9]

In above application examples, process from above-mentioned first printing ink composition to recording medium that adhere to and make above-mentioned second oil The surface temperature for the recording medium in process that ink composition adheres to recording medium is 45 DEG C hereinafter, to record after each process In the reheating process that medium is heated, the surface temperature of recording medium can be set as 70 DEG C or more.

According to above application examples, the process for adhering to the first printing ink composition to recording medium and make the second printing ink composition The surface temperature for the recording medium in process adhered to recording medium is 45 DEG C hereinafter, carrying out after each process to recording medium In the reheating process of heating, the surface temperature of recording medium is 70 DEG C or more, thus further decreases the blocking of nozzle, energy Enough take into account the reliability of erasibility and resistance to blocking.

[application examples 10]

In above application examples, any number of conduct in multivalent metal salt, cationic resin or organic acid can be included Agglutinant contained by above-mentioned reaction solution.

According to above application examples, comprising any number of as agglutination in multivalent metal salt, cationic resin or organic acid Thus agent further increases erasibility.

Detailed description of the invention

Fig. 1 is the schematic cross sectional view for schematically illustrating ink-jet recording apparatus.

Symbol description

1: ink-jet recording apparatus；2: ink gun；3:IR heater；4: laminate heater；5: solidification heater；6: cooling wind Fan；7: pre-heater；8: draught fan；M: recording medium.

Specific embodiment

The preferred embodiment of the present invention will be described below.Embodiment described below is to of the invention one The embodiment that a example is illustrated.In addition, further including not changing this hair the present invention is not limited to following embodiment The various modifications example implemented in the range of bright purport.

The one side of the ink group of present embodiment, the reaction solution being aggregated for being reacted with the ingredient with printing ink composition Adhere to together to recording medium, above-mentioned ink group is characterized in that having: the first printing ink composition, it includes color materials, fixing tree Rouge and resin dissolubility solvent；Second printing ink composition, it is and above-mentioned it includes color material, fixing resin and resin dissolubility solvent Identical colour system ink, the content of above-mentioned color material are less than above-mentioned first printing ink composition to first printing ink composition each other, wherein above-mentioned Second printing ink composition fixing resin content more than above-mentioned first printing ink composition fixing resin content, above-mentioned second Content of the content of the resin dissolubility solvent of printing ink composition more than the resin dissolubility solvent of above-mentioned first printing ink composition.

The one side of the recording method of present embodiment, which is characterized in that using according to the present embodiment ink group into Row, above-mentioned recording method have: the process for adhering to above-mentioned reaction solution to recording medium；Make above-mentioned first printing ink composition to note The process of recording medium attachment；And the process for adhering to above-mentioned second printing ink composition to recording medium.

In the following, for an example of ink group and recording method according to the present embodiment, according to carrying out the record side The recording device of method, printing ink composition are (hereinafter, also referred to as " ink ".), reaction solution and recording medium, the sequence of recording method into Row explanation.

In addition, " occupation rate " is the value being calculated by following formula (1) in this specification.

Occupation rate (%)={ practical lettering points/(vertical resolution ratio × horizontal resolution ratio) } × 100 ... (1) are (" real in formula Border lettering points " are that the practical lettering of per unit area is counted, and " vertical resolution ratio " and " horizontal resolution ratio " is respectively per unit area Resolution ratio.)

1. each constituted

1.1. recording device

For an example of the recording device of the recording method for implementing present embodiment, ink-jet recording apparatus is enumerated It is illustrated.In addition, an example of the recording device as the recording method that can be used in present embodiment, is not limited to Ink-jet recording apparatus.

It is illustrated referring to an example of the attached drawing to ink-jet recording apparatus used in present embodiment.Fig. 1 is signal Ground shows the schematic cross sectional view of ink-jet recording apparatus.As shown in Figure 1, ink-jet recording apparatus 1 have ink gun 2, IR heater 3, Laminate heater 4, solidification heater 5, cooling fan 6, pre-heater 7 and draught fan 8.Ink-jet recording apparatus 1 has in figure The control unit being not shown implements control to the whole movement of ink-jet recording apparatus 1 using control unit.

Ink gun 2 be recording medium M is sprayed and is adhered to printing ink composition, reaction solution device.

Ink gun 2, which has, sprays printing ink composition, the nozzle (not shown in FIG.) of reaction solution.Oil is sprayed as from nozzle The mode of ink, such as can enumerate: applying strong electrical field between nozzle and acceleration electrode positioned at the front of nozzle, connect from nozzle The ink for spraying droplet-like continuously corresponds to record information signal during the drop of ink splashes between deflecting electrode and sprays Mode (electrostatic attraction mode) out；By applying pressure to ink using pony pump, keep nozzle mechanical using quartz crystal etc. Ground vibration, forcibly sprays the mode of the drop of ink；Apply pressure simultaneously to ink using piezoelectric element and record information is believed Number, spray the mode (piezo electrics) that the drop of ink is recorded；Make ink using microelectrode according to record information signal Foamable sprays the mode (thermojet mode) etc. that the drop of ink is recorded.

As ink gun 2, Line type inkjet head can be used, either in serial type ink-jet head.

Wherein, the ink-jet recording apparatus for having serial type ink-jet head is, by repeatedly being made recording ink gun phase Recording medium is relatively moved and the scanning (path) for spraying printing ink composition carrys out the device of implementation record.For serial type The concrete example of ink gun can enumerate ink gun and be equipped on the width direction (conveying direction with recording medium in recording medium It is crisscross) on the balladeur train that moves, ink gun is moved along with the movement of balladeur train, to spray drop in recording medium Example.

On the other hand, the ink-jet recording apparatus for having Line type inkjet head is, by once being made recording ink gun It is relatively moved relative to recording medium and the scanning (path) for spraying printing ink composition carrys out the device of implementation record.For line The concrete example of ink gun can enumerate the width that ink gun is formed wider than recording medium, in the state that record is not moved with head The example of drop is sprayed in recording medium.

In the present embodiment, as ink-jet recording apparatus 1, using the ink-jet recording apparatus for having serial type ink-jet head, The ink gun 2 using piezo electrics is used as the mode for spraying ink from nozzle.

Ink-jet recording apparatus 1 has for being heated when spraying printing ink composition from ink gun 2 to recording medium M IR heater 3 and laminate heater 4 (primary heating or primary drying).In the present embodiment, in aftermentioned printing ink composition When heating in attachment process to recording medium M, at least one party in IR heater 3 and laminate heater 4 is used.

In addition, can be heated from 2 side of ink gun to recording medium M when using IR heater 3.Ink gun as a result, 2 are also easy to be heated simultaneously, but compared with the case where laminate heater 4 etc. is heated from the back side of recording medium M, can not It is influenced and is heated up by the thickness of recording medium M.In addition, when using laminate heater 4 when heating to recording medium M, Recording medium M can be heated from 2 side opposite side of ink gun.Ink gun 2, which compares, as a result, is difficult to be heated.

Preferably, the upper limit of the surface temperature of the recording medium M realized by IR heater 3 and laminate heater 4 is 45 DEG C Hereinafter, more preferably 40 DEG C hereinafter, more preferably 35 DEG C or less.Moreover it is preferred that be the surface temperature of recording medium M Lower limit is at 25 DEG C or more, more preferably 28 DEG C or more, more preferably 30 DEG C or more.It is heated as a result, from IR heater 3 and pressing plate The radiant heat that device 4 is born is less or is not subject to radiant heat, so the drying and group of the printing ink composition being able to suppress in ink gun 2 At variation, inhibited the case where the inner wall of ink gun 2 is deposited with ink, resin.Furthermore it is possible to early stage fixed ink, energy Enough improve image quality.

Solidify heater 5 make to be attached to recording medium M printing ink composition is dry and solidification (reheating is secondary dry It is dry).Solidify heater 5 by thering is the recording medium M of image to heat record, makes moisture contained in printing ink composition etc. More quickly evaporation is dispersed, and forms ink film using the resin of resin microparticle contained in printing ink composition.In this way, recording The medium M ink film that oils is fixed (bonding) securely and keeps film forming excellent, and the figure of excellent high image quality can be obtained with the short time Picture.Preferably, the upper limit of the surface temperature of the recording medium M realized by solidification heater 5 is 120 DEG C hereinafter, more preferably 100 DEG C hereinafter, more preferably 90 DEG C or less.Moreover it is preferred that the lower limit of the surface temperature of recording medium M is 60 DEG C or more, more Preferably 70 DEG C or more, more preferably 80 DEG C or more.By making temperature be in the range, high draw can be obtained with the short time The image of matter.

Ink-jet recording apparatus 1 also can have cooling fan 6.Keep the printing ink composition for being recorded in recording medium M dry Afterwards, the printing ink composition on recording medium M is cooled down using cooling fan 6, so as to the close property on recording medium M Ink film is formed well.

In addition, ink-jet recording apparatus 1 can also have before for recording medium M attachment printing ink composition, reaction solution in advance (preheating) pre-heater 7 that first recording medium M is heated.Moreover, recording device 1 can also have draught fan 8 with Dry the printing ink composition for being attached to recording medium M, reaction solution more efficiently.

1.2. printing ink composition

Then, the printing ink composition for the ink group for constituting present embodiment is illustrated.Constitute the oil of present embodiment The first printing ink composition and the second printing ink composition of ink group separately include color material, fixing resin and resin dissolubility solvent.

Wherein, in the present embodiment, the first oil will be set as according to the ink composition more than the content of the color material of quality criteria Ink composition (dense ink) will compare the ink group of color material according to the content of the color material of quality criteria less than the first printing ink composition It closes object and is set as the second printing ink composition (light ink).

In addition, in ink group according to the present embodiment, the first printing ink composition and the second printing ink composition phase each other With colour system ink." identical colour system " refers to " substantially having identical hue angle ", refers to according to the first printing ink composition and second The difference that printing ink composition is recorded in the hue angle ∠ H ° of each record image in the recording medium of white is within 30 °.Form and aspect Angle ∠ H ° is defined in CIELAB color space, according to ∠ H °=tan^-1(b*/a*)+180 (the case where a* < 0) or ∠ H °= tan^-1(b*/a*)+360 (the case where a* > 0), are acquired.

A* and b* indicates to perceive chromaticity index defined in CIELAB color space.The dense ink of such identical colour system and The combination of light ink, such as the combination of cyan ink and pale cyan ink (also referred to as photo cyan ink), magenta can be enumerated Combination, Yellow ink and combination of yellowish color ink of ink and light magenta ink (also referred to as photo magenta ink) etc..In addition, Only the dense ink comprising mutually homochromy material and light ink can be regarded as identical colour system ink each other respectively.

In addition, the printing ink composition for constituting the ink group of present embodiment is characterized in that, according to quality criteria, the second oil The content of the fixing resin of ink composition is more than the content of the fixing resin of the first printing ink composition, according to quality criteria, second The content of the resin dissolubility solvent of printing ink composition is more than the content of the resin dissolubility solvent of the first printing ink composition.

In the following, ingredient and the ingredient that may include contained by printing ink composition to the ink group for constituting present embodiment carry out It explains in detail.

Furthermore it is preferred that the printing ink composition for constituting the ink group of present embodiment is aqueous inkjet ink composition.Its In, " water system " inkjet ink composition in the present invention is, with water for main solvent, without using organic solvent as primary solvent Composition.Preferably, the content of the organic solvent in printing ink composition is 30 mass % relative to 100 mass % of its composition Hereinafter, more preferably 25 mass % are hereinafter, particularly preferably 20 mass % or less.Preferably, printing ink composition (100 mass %) In water content be 50 mass % or more, more preferably 60 mass % or more, particularly preferably 70 mass % or more.

1.2.1. color material

In the present embodiment, printing ink composition includes color material.As color material, it is able to use dyestuff and any in pigment Side, but pigment has and is difficult to the property faded relative to light, gas etc., therefore it is preferable to use.Record is formed in using pigment to be situated between Image in matter, not only image quality is excellent, but also water resistance, gas resistance, light resistance etc. are excellent, have good keeping qualities.The property is special It is not significant in the recording medium for being formed in ink nonabsorbable or low absorption.In addition, in the present embodiment, First printing ink composition can also separately include mutually homochromy material with the second printing ink composition, also may include different color materials.

It as the pigment being able to use in present embodiment, is not specially limited, inorganic pigment, You Jiyan can be enumerated Material.As inorganic pigment, in addition to titanium oxide and iron oxide, it is able to use through method well known to contact method, oven process, thermal method etc. The carbon black being fabricated.On the other hand, as organic pigment, azo pigments is able to use (comprising azo lake, insoluble azo Pigment, condensed azo pigment, chelate azo pigments etc.), polycyclic pigment is (for example, phthalocyanine color, pigment, purple cyclic ketones face Material, anthraquinone pigment, quinophthalone pigments etc.), nitropigments, nitroso pigments, nigrosine etc..

Carbon black can be enumerated as the mineral black in the concrete example for the pigment being able to use in present embodiment, as charcoal It is black, it is not particularly limited, such as furnace black, lampblack, acetylene black or channel black can be enumerated etc. (C.I. black pigment 7), furthermore As commercially available product can enumerate No.2300,900, MCF88, No.20B, No.33, No.40, No.45, No.52, MA7, MA8, MA77, MA100, No.2200B etc. (the above trade name, Mitsubishi chemical Co., Ltd's system), black pigment (color black) FW1, FW2, FW2V, FW18, FW200, S150, S160, S170, Pritex35, U, V, 140U, it is goth black 6,5,4A, 4,250 etc. (more than Trade name, goldschmidt chemical corporation system), ConductexSC, Rarben1255,5750,5250,5000,3500,1255,700 etc. (with Upper trade name, Colombia's carbon corporation), Regal400R, 330R, 660R, MogulOGUL L, Monarch700,800, 880,900,1000,1100,1300,1400, Elftex12 etc. (the above trade name, Cabot Co., Ltd's system).

White pigment is not particularly limited, such as can enumerate C.I. Pigment white 6,18,21, titanium oxide, zinc oxide, sulphur Change the white inorganic pigment of zinc, antimony oxide, magnesia and zirconium oxide.In addition to the white inorganic pigment, additionally it is possible to use white Hollow resin particles and the white organic pigments such as polymeric particles.

As pigment used in Yellow ink, be not particularly limited, for example, can enumerate C.I. pigment yellow 1,2,3,4, 5、6、7、10、11、12、13、14、16、17、24、34、35、37、53、55、65、73、74、75、81、83、93、94、95、97、 98、99、108、109、110、113、114、117、120、124、128、129、133、138、139、147、151、153、154、 167、172、180。

As the used pigment of magenta ink, be not particularly limited, for example, can enumerate C.I. paratonere 1,2,3,4,5, 6、7、8、9、10、11、12、14、15、16、17、18、19、21、22、23、30、31、32、37、38、40、41、42、48(Ca)、48 (Mn), 57 (Ca), 57:1,88,112,114,122,123,144,146,149,150,166,168,170,171,175,176, 177,178,179,184,185,187,202,209,219,224,245 or C.I. pigment violet 19,23,32,33,36,38,43, 50。

As pigment used in cyan ink, be not particularly limited, for example, can enumerate C.I. pigment blue 1,2,3,15, 15:1,15:2,15:3,15:34,15:4,16,18,22,25,60,65,66, C.I. bat indigo plant 4,60.

In addition, be not particularly limited as pigment used in the colored ink other than pinkish red, cyan and yellow, such as Can enumerate C.I. pigment Green 7,10, C.I. pigment brown 3,5,25,26, C.I. pigment orange 1,2,5,7,13,14,15,16,24, 34、36、38、40、43、63。

Preferably, all-mass (100 matter of the content of pigment contained by printing ink composition relative to printing ink composition Measure %) it is 0.1 mass % or more, 15 mass % hereinafter, more preferably 0.5 mass % or more, 10 mass % is hereinafter, further preferably For 1.0 mass % or more, 7 mass % or less.

In order to which above-mentioned pigment is applied to printing ink composition, need to make pigment that can steadily disperse to keep in water. As its method, can enumerate be dispersed in the dispersant resins such as water-soluble resin and/or water-dispersed resin method (under Face will be referred to as " resin dispersion pigment " using the pigment of this method dispersion.), be dispersed in water soluble surfactant active and/or moisture The method in the surfactant of property surfactant is dissipated (in the following, by " surfactant is referred to as using the pigment of this method dispersion Disperse pigment ".), to pigment particle surface chemically/physically import hydrophilic functional group to without above-mentioned resin or The method that can disperse and/or be dissolved in the water in the case where the dispersing agents such as person's surfactant is (in the following, will be using this method point Scattered pigment is referred to as " surface treated pigments ".) etc..In the present embodiment, printing ink composition is able to use above-mentioned resin point Dispersed pigment, surfactant-dispersed pigment, either in surface treated pigments, also can with mixing, there are many face as needed The mode of material come using.

As the dispersant resin for resin dispersion pigment, polyvinyl alcohol, polyvinylpyrrolidone can be enumerated Class, polyacrylic acid, AA-AN copolymerization object, vinyl acetate-acrylate copolymer, acrylic acid-acrylic ester copolymerization Object, Styrene-acrylic copolymer, Styrene-methyl Acrylic Acid Copolymer, styrene-t-acrylic ester copolymer Object, styrene-α-methylstyrene-acrylic copolymer, styrene-α-methylstyrene-acrylic acid-acrylic ester copolymerization Object, styrene-maleic acid copolymer, styrene-anhydrous maleic acid copolymer, vinylnaphthalene-acrylic copolymer, vinylnaphthalene-horse Come acid copolymer, vinylacetate-maleate copolymer, vinyl acetate-crotonic acid copolymer, vinyl acetate-acrylic Acid copolymer etc. and their salt.Wherein, particularly preferably, monomer with hydrophobic functional groups with there is hydrophilic functional group The copolymer of monomer, the polymer that is made of the monomer together with hydrophobic functional groups and hydrophilic functional group.As altogether The mode of polymers is also able to use random copolymer, block copolymer, alternate copolymer, formula either in graft copolymer.

As the salt, ammonia, ethamine, diethylamine, triethylamine, propylamine, isopropylamine, di-n-propylamine, butylamine, different can be enumerated The salt of the alkali compounds such as butylamine, diethanol amine, triethanolamine, triisopropanolamine, aminomethylpropanol, morpholine.These alkalinity The additive amount of compound if it is the neutralization equivalent of the dispersant resin more than, then be not specially limited.

Preferably, the molecular weight of above-mentioned dispersant resin, as weight average molecular weight 1,000 to 100,000 range, More preferably 3,000 to 10,000 range.It is in above range by molecular weight, can get color material in water stable Dispersion, furthermore easily controllable viscosity etc. when being applied to printing ink composition.

Commercially available product can also be used as above-mentioned dispersant resin.Specifically, can enumerating Joncryl67, (weight is equal Molecular weight: 12,500, acid value: 213), Joncryl678 (weight average molecular weight: 8,500, acid value: 215), (weight is equal by Joncryl586 Molecular weight: 4,600, acid value: 108), Joncryl611 (weight average molecular weight: 8,100, acid value: 53), Joncryl680 (divides equally again Son amount: 4,900, acid value: 215), Joncryl682 (weight average molecular weight: 1,700, acid value: 238), Joncryl683 (divides equally again Son amount: 8,000, acid value: 160), Joncryl690 (weight average molecular weight: 16,500, acid value: 240) (the above trade name, Japan BASF Co. Ltd. system) etc..

In addition, alkylsulfonate, alpha-olefin can be enumerated as the surfactant for surfactant-dispersed pigment Sulfonate, alkylbenzene sulfonate, alkylnaphthalene sulfonate, acyl methyl taurine salt, dialkyl sulfosuccinates, alkylsurfuric acid It is ester salt, sulphation alkene, polyoxyethylene alkyl ether sulfuric acid, alkyl phosphate salt, polyoxyethylene alkyl ether phosphate salt, sweet The both sexes tables such as the anionic surfactants such as oily monoesters phosphate ester salt, Fixanol, alkane propylhomoserin salt, alkyl dimethyl betaine It is face activating agent, polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyxyethylated ester, polyoxyethylene alkylamide, sweet The nonionic surfactants such as oily Arrcostab, sorbitan Arrcostab.

The additive amount of above-mentioned dispersant resin or above-mentioned surfactant relative to pigment, relative to 100 mass parts of pigment, Preferably 1 mass parts are to 100 mass parts, more preferably 5 mass parts to 50 mass parts.By setting it as the range, it can be ensured that face The dispersion stabilization of material in water.

In addition, as surface treated pigments, as hydrophilic functional group ,-OM ,-COOM ,-CO- ,-SO can be enumerated₃M、- SO₂NH₃、-RSO₃M、-PO₃HM、-PO₃M₃、-SO₃NHCOR、-NH₃、-NR₃(wherein, the M in formula indicates hydrogen atom, alkali metal, ammonium Or organic ammonium, R indicate the alkyl of carbon number 1 to 12, can have the phenyl of substituent group or can have the naphthalene of substituent group.) etc.. These functional groups are direct and/or are grafted to pigment particle surface via other bases, to physically and/or chemically lead Enter.As the base of multivalence, alkylidene that carbon number is 1 to 12 can be enumerated, the phenylene that also can have substituent group, can also be had The naphthylene etc. of substituted base.

Moreover it is preferred that the surface treated pigments be surface-treated using the inorganic agent comprising Sulfur so that- SO₃M and/or-RSO₃(M is ion pair and indicates hydrogen ion, alkali metal ion, ammonium ion or organoammonium ions M.) chemical bonding In the pigment of the pigment particle surface, that is, the pigment, which does not have active proton, makes pigment without the reactivity with sulfonic acid Be scattered in that pigment is insoluble or the solvent of indissoluble in, next utilize amido sulfuric acid salt or the complex compound of sulfur trioxide Huang and tertiary amine It is surface-treated so that-SO₃M and/or-RSO₃M is chemically combined at the particle surface, to be made to disperse and/or dissolve In the pigment of water.

As making at the surface of the functional group or its salt directly or via the base surface that is grafted on granules of pigments of multivalence Reason means, can be using various well known surface treatment means.Such as can enumerate by ozone, hypochlorite of soda solution effects in Commercially available oxidized black, to carbon black further progress oxidation processes, to the means (example of its surface further progress hydrophilicity-imparting treatment Such as, Japanese patent application discloses flat 7-258578 bulletin, Japanese patent application discloses flat 8-3498 bulletin, Japan is special Benefit application discloses flat 10-120958 bulletin, Japanese patent application discloses flat 10-195331 bulletin, Japan Patent Shen Flat 10-237349 bulletin please be disclose), carbon black is handled using 3- amino-N- alkyl substituted pyridines bromide hand Section is (for example, Japanese patent application discloses flat 10-195360 bulletin, Japanese patent application discloses flat 10-330665 public affairs Report), make organic pigment be scattered in that organic pigment is insoluble or the solvent of indissoluble in, import sulphur to pigment particle surface using sulfonating agent (for example, Japanese patent application discloses flat 8-283596 bulletin, Japanese patent application discloses flat 10- to the means of base No. 110110 bulletins, Japanese patent application disclose flat 10-110111 bulletin), be scattered in organic pigment and sulfur trioxide It is formed in the basic solvent of complex compound, the surface of organic pigment handle imports sulfo group or sulphur by adding sulfur trioxide Means (for example, Japanese patent application discloses flat 10-110114 bulletin) of amino etc., but table is used for used in the present invention The method of producing of surface treatment pigment is not limited to these means.

Functional group with the grafting of a granules of pigments is either single being also possible to is a variety of.The functional group of grafting Type and its degree are appropriate whiles considering the drying property etc. before the dispersion stabilization in ink, colour saturation and ink gun Determination.

Water is scattered in as making resin as described above disperse pigment, surfactant-dispersed pigment, surface treated pigments In method add face for surfactant-dispersed pigment for resin dispersion pigment addition pigment, water and dispersant resin Material, water and surfactant add surface treated pigments and water for surface treated pigments, water are furthermore respectively added as needed Solubleness organic solvent and neutralizer etc., in ball mill, sand mill, grinding mill (attritor), roller mill, blender (agitator), Henschel mixer, rubber mill, ultrasonic homogenizer, injector-type mill, micronizer (Ang mill) etc. It is carried out in the dispersion machine used in the past.In this case, as the partial size of pigment, being dispersed to average grain diameter becomes 20nm extremely Until the range of 500nm, it is more preferably dispersed to the range as 50nm to 200nm, this dispersion in the water for ensuring pigment It is also preferred in terms of stability.

1.2.2. it is fixed resin

In the present embodiment, printing ink composition contains fixing resin, the content of the fixing resin of the second printing ink composition More than the content of the fixing resin of the first printing ink composition.Fixing resin, which has, solidifies printing ink composition and by ink solidification Object is securely fixed in the effect in recording medium.In the present embodiment, fixing resin can be comprising using in present embodiment Printing ink composition solvent in indissoluble perhaps insoluble resin be made into microparticulate and disperse (i.e. emulsion state or Suspended state), also referred to as " adhesive solids ingredient ", " resin emulsion ".

It as resin is fixed used in present embodiment, is not particularly limited, but except as above-mentioned dispersant resin Resin other than, such as (methyl) acrylic acid, (methyl) acrylate, acrylonitrile, cyanoacrylate, acryloyl can be enumerated Amine, alkene, styrene, vinylacetate, vinyl chloride, vinyl alcohol, vinyl ethers, vinyl pyrrolidone, vinylpyridine, second Homopolymer or copolymer, the fluororesin and natural resin of alkene carbazole, vinyl imidazole and vinylidene chloride.Wherein, preferably (first Base) it is at least any in (methyl) acrylic monomer such as acrylic acid, (methyl) acrylate, acrylonitrile, cyanoacrylate Homopolymer or copolymer acrylic resin.In acrylic resin, preferably (methyl) acrylic monomer and second The copolymer of alkene monomer.It is not intended to limit as vinyl monomer, but styrene can be enumerated etc., particularly preferably (methyl) third The Styrene-acrylic copolymer system resin of the copolymer of olefin(e) acid system monomer and styrene.In addition, above-mentioned copolymer can also be with For formula either in random copolymer, block copolymer, alternate copolymer and graft copolymer.In addition, as resin, except upper Polyurethane series resin, polyester based resin, polyether system resin are further preferably used other than stating.

In addition, fixing resin can be the macromolecule of straight chain or branch-like, it is also possible to three-dimensional cross-linked macromolecule, preferably For three-dimensional cross-linked macromolecule.

The above-mentioned resin that microparticle state can be obtained by method as shown below, can be any method, can also To combine multiple methods as needed.As its method, it can enumerate and mix and polymerize in the monomer for constituting desired resin The method of (i.e. emulsion polymerization) polymerization catalyst (polymerization initiator) and dispersing agent dissolves the resin with hydrophilic parts In water-miscible organic solvent and the solution is mixed to the side for passing through afterwards obtain after the removal water-miscible organic solvent such as distillation in water Resin is dissolved in water-insoluble organic solvent and the solution is mixed together to the side obtained in aqueous solution together with dispersing agent by method Method etc..Above-mentioned method can suitably be selected according to type/characteristic of the resin used.It is able to use as in dispersion resin Dispersing agent, be not specially limited, but anionic surfactant can be enumerated (for example, neopelex, lauryl Sodium phosphate, polyoxyethylene alkyl ether sulfate ammonium salt etc.), nonionic surfactant is (for example, polyoxyethylene alkyl ether, polyoxy Vinyl alkyl ester, Polyoxyethylene Sorbitan acid esters, polyoxyethylene alkyl phenyl ether etc.), it can be by above-mentioned dispersing agent list Solely or mixing is two or more uses.

As resin as described above, with microparticle state (emulsion state, suspended state) use, moreover it is possible to It is enough to use the resin obtained in well known material/method.For example, it is also possible to announce clear 62-1426 public affairs using Japanese Patent Report, Japanese patent application discloses flat 3-56573 bulletin, Japanese patent application discloses flat 3-79678 bulletin, Japan is special Benefit application discloses flat 3-160068 bulletin, Japanese patent application discloses the resins of the records such as flat 4-18462 bulletin.This Outside, additionally it is possible to use commercially available product, such as Microgel E-1002, Microgel E-5002 (the above trade name, day can be enumerated This coating Co. Ltd. system), Voncoat 4001, Voncoat 5454 (the above trade name, big Japanese ink chemical industry strain formula Commercial firm's system), SAE1014 (trade name, Zeon Corp's system), Sybinol SK-200 (trade name, Saiden chemistry strain Formula commercial firm system), Jurymer AT-613 (trade name, Toagosei Co., Ltd's system), Vinyblan 700 (trade name, day letter Chemical industry Co. Ltd. system), Joncryl7100, Joncryl390, Joncryl711, Joncryl511, Joncryl7001, Joncryl632、Joncryl741、Joncryl450、Joncryl840、Joncryl74J、Joncryl HRC-1645J、 Joncryl734、Joncryl852、Joncryl7600、Joncryl775、Joncryl537J、Joncryl1535、Joncryl PDX-7630A、Joncryl352J、Joncryl352D、Joncryl PDX-7145、Joncryl538J、Joncryl7640、 Joncryl7641, Joncryl631, Joncryl790, Joncryl780, JONCRYL7610 (the above trade name, Japanese BASF Co. Ltd. system) etc..

Fixing resin also may include compound resin.Compound resin is as the resin for constituting fixing, by the list for constituting resin The mutually different two or more resin of the composition (either one of type, content than in) of body ingredient is constituted, and does not limit this Two or more resins constitutes which position of fixing resin.Two or more resins is not limited to can be discontinuous on its boundary The resin that resin is constituted is distinguished on ground, and be also possible to monomer component constitutes continuously different resins.

In particular, in the case where using core shell resin as fixing resin, wherein will be two or more in core shell resin One of resin be used as core resin, using another as shell resin, core resin is mainly set as to composition resin microparticle The resin of central portion, by shell resin mainly be set as constitute resin microparticle peripheral portion resin, resin peripheral portion in Centre portion can change the characteristic of resin respectively, be preferred in this regard.In this case, shell resin constitutes fixing resin At least part of peripheral portion.Wherein, core shell resin is described as an example of compound resin, but is not limited to core shell tree Rouge then can also play same effect if it is compound resin.Since the core and shell of core shell resin are independent, it can be crosslinked Degree, glass transformation temperature are controlled, therefore from the viewpoint of the dissolubility that can easily be accommodated resin, preferably core shell resin.

In addition, for being not the resin of core shell resin, it can be with the glass transformation temperature of resin, the degree of crosslinking To adjust dissolution time.And, however it is not limited to glass transformation temperature, crosslinking degree, the monomer that can be used with resins synthesis The compositions such as type, amount be adjusted.

With microparticle state using fixing resin, from the storage stability/ejection for ensuring printing ink composition From the perspective of reliability, it is preferable that its average grain diameter is 5nm or more 400nm range below, more preferably 50nm or more 200nm range below.The average grain diameter of resin microparticle is in the range, and thus film forming is excellent, and even if agglutination It not will form biggish piece, therefore can reduce the blocking of nozzle.In addition, as long as no especially expressing, it is flat in this specification Equal partial size is exactly the partial size of volume reference.As measurement method, such as can utilize former for measurement with dynamic light scattering theory The particle size distribution measurement device of reason measures.As such particle size distribution measurement device, such as a day machine dress strain can be enumerated " the Mai Qike UPA " of formula commercial firm etc..

The glass transformation temperature (Tg) of fixing resin is for example preferably -20 DEG C or more 100 DEG C hereinafter, more preferably -10 DEG C Above 80 DEG C hereinafter, further preferably 0 DEG C or more 76 DEG C or less.

All-mass (100 matter for being fixed the lower limit of total content of the content of resin, relative to printing ink composition Measure %), it converts and calculates according to solid component, preferably 0.1 mass % or more, more preferably 0.5 mass % or more are further excellent It is selected as 2 mass % or more, particularly preferably 4 mass % or more.In addition, the upper limit of total content for the content of resin, phase For the all-mass (100 mass %) of printing ink composition, preferably 15 mass % hereinafter, more preferably 10 mass % hereinafter, Further preferably 7 mass % are hereinafter, particularly preferably 5 mass % or less.Be fixed resin content within the above range, thus The reliability that can ensure resistance to blocking when recording, can in the recording medium in ink nonabsorbable or low absorption Form the excellent image of erasibility.

In addition, in the present embodiment, the content of color material is less than determining for the second printing ink composition of the first printing ink composition The content of shadow resin is more than the first printing ink composition, specifically, the content and first of the fixing resin of the second printing ink composition The content of the fixing resin of printing ink composition is compared, and preferably more 0.5 mass % or more, 5 mass % are hereinafter, more preferably more 1.0 4 mass % of quality % or more is hereinafter, further preferably more 1.5 mass % or more, 3.5 mass % or less.By being in the model It encloses, is particular enable to improve the low erasibility for occupying the printed article in region using the second printing ink composition.Furthermore it is possible to ensure The reliability of resistance to blocking when the record of the first more printing ink composition of the content of color material.

In addition, in second printing ink composition of the content of color material less than the first printing ink composition, it is preferable that the second ink Fixing resin contained by composition is, in the environment of 25 DEG C, with the mass ratio of 1:1 by 0.3M magnesium sulfate solution and by water When resin liquid obtained by middle 1 mass % of dispersion resin stirs 1 minute, reactivity of the variation of average grain diameter less than 5 times is lower Resin.By, using the lower resin of reactivity, being reacted in ink composition with reaction solution in the second printing ink composition and forming figure When picture, formed a film in a manner of being fixed resin covering after color material first precipitates (reaction), thus can be realized it is smooth at membranization, into One step improves erasibility.In addition, the average grain diameter in this specification is exactly the partial size of volume reference as long as no especially expressing. As measurement method, for example, can be carried out using by the particle size distribution measurement device of measuring principle of dynamic light scattering theory Measurement.As such particle size distribution measurement device, such as " Mai Qike UPA " that Nikkiso Company Limited can be enumerated etc..

Moreover, in the second printing ink composition, as fixing resin, it is preferable that comprising molten with aftermentioned resin dissolubility The difference of the SP value of agent is the resin within 5, and more preferably the difference comprising SP value is the resin within 4, further preferably includes SP value Difference be 3 within resin, particularly preferably comprising SP value difference be 2 within resin.The SP value and resin for being fixed resin dissolve Property solvent SP value difference it is smaller, fixing resin is more easily soluble in resin dissolubility solvent, it can be ensured that resistance to stifled when record The reliability of plug.Further, since smooth film forming on the recording medium is excellent, therefore it is capable of forming the excellent figure of erasibility Picture.

In addition, if comprising and resin dissolubility solvent SP value difference be 5 within fixing resin, also may include The difference of SP value is mutually more than 5 resin, but in the reliability this point for ensuring resistance to blocking when recording, it is preferable that all fixings Resin is and the difference of the SP value of resin dissolubility solvent is the resin within 5.

Wherein, in the present specification, " SP value ", which is referred to as, mutually dissolves parameter (Solubility Parameter), can also claim Make solubility parameter.For solvent, the calculating SP value (δ) that SP value is able to use Hildebrand shown in numerical expression 1 passes through It calculates and calculates, for resin, resin is added to the solvent of known SP value, so that the resin solid content concentration in liquid becomes The lower value of dispersible SP value can be set as resin SP value by 0.5 mass %, the dispersion stabilization of visual confirmation resin.

[numerical expression 1]

1.2.3. resin dissolubility solvent

In the present embodiment, printing ink composition is characterized in that: it include resin dissolubility solvent, according to quality criteria, The content of the resin dissolubility solvent of second printing ink composition (light ink) is more molten than the resin of the first printing ink composition (dense ink) The content of solution property solvent is more.It in the present embodiment, include resin dissolubility solvent by printing ink composition, on the recording medium It dissolves the resin of recording medium and promotes to be capable of forming at membranization erasibility and the excellent image of image quality.Furthermore it is possible to reduce Spray blocking when printing ink composition.

In the present specification, resin dissolubility solvent is the solvent of the characteristic with dissolving resin, specifically, relatively In 100 grams of solvent, the fixing resin that the printing ink composition of 1 gram of present embodiment contains is added, it is fixed when being stirred 1 hour with 80 DEG C The dissolution of shadow resin, the invisible fixing resin of observation becomes blocky, particle by visual observation.

As resin dissolubility solvent, it is preferable that also there is intermiscibility relative to water contained in ink.Specifically, Preferably, at 25 DEG C, relative to water mass parts, the i.e. solubility of solvent that dissolves of 100 mass parts for 0.5 mass % with On.

More specifically, as alcohols, such as 2-methyl-1-butene alcohol, 3- methyl-1-butanol, 1- hexanol, 2- can be enumerated Methyl-1-pentene alcohol, 4- methyl -2- amylalcohol, 2- (benzyloxy) ethyl alcohol etc..

As ethers, such as propylene oxide, furans can be enumerated etc..

As ketone, such as methyl-n-butyl ketone, 2- methyl -4- pentanone, Mesityl oxide isophorone can be enumerated etc..

As esters, such as formic acid n-propyl, formic acid N-butyl, formic acid iso-butyl, n-propyl acetate, acetic acid can be enumerated The secondary own ester of N-butyl, isobutyl acetate, sec-Butyl Acetate, acetic acid, ethyl propionate, butyl propionate, methyl butyrate, butyl butyrate, Isobutyl isobutyrate, acetic acid 2- fourth 2-ethoxyethyl acetate etc..

As nitrogenous compound, such as 1- nitropropane, 2- nitropropane can be enumerated etc..

As sulfur-bearing Huang compound, such as methyl sulfide, diethyl sulfide, thiophene can be enumerated etc..

As cyclic annular esters, such as following chemical formula (1) compound represented can be enumerated.

[changing 1]

(in chemical formula (1), R¹Indicate that the alkyl of hydrogen or carbon number 1 to 4, d indicate 0 to 3

Integer.Furthermore the alkyl is either straight-chain is also possible to branch-like.)

As formula (1) compound represented, beta-propiolactone, gamma-butyrolacton, δ-valerolactone, 6-caprolactone, β-fourth can be listed The hydrogen of the ring-type esters such as lactone, gamma-valerolactone (lactone) and the methylene adjacent with their carbonyl is by the alkane of carbon number 1 to 4 The compound etc. that base replaces.

As Alkoxyalkylamino class, such as following formula (2) compound represented can be enumerated.

R²O-CH₂CH₂-CO-NR³R⁴……(2)

(in formula (2), R²Indicate the alkyl of carbon number 1 to 4, R³And R⁴Separately indicate the alkyl of carbon number 1 to 2.)

Formula (2) compound represented is β-alkoxypropan amide compound, such as can enumerate 3- methoxyl group-N, N- diformazan Base propionamide, 3- methoxyl group-N, N- diethyl propionamide, 3- methoxyl group-N, N- Methylethyl propionamide, 3- ethyoxyl-N, N- Dimethylpropionamide, 3- ethyoxyl-N, N- diethyl propionamide, 3- ethyoxyl-N, N- Methylethyl propionamide, 3-n- fourth oxygen Base-N, N- dimethylpropionamide, 3-n- butoxy-N, N- diethyl propionamide, 3-n- butoxy-N, N- Methylethyl propionyl Amine, 3-n- propoxyl group-N, N- dimethylpropionamide, 3-n- propoxyl group-N, N- diethyl propionamide, 3-n- propoxyl group-N, N- first Base ethyl propionamide, 3-iso- propoxyl group-N, N- dimethylpropionamide, 3-iso- propoxyl group-N, N- diethyl propionamide, 3- Iso- propoxyl group-N, N- Methylethyl propionamide, 3-tert- butoxy-N, N- dimethylpropionamide, 3-tert- butoxy-N, N- diethyl propionamide, 3-tert- butoxy-N, N- Methylethyl propionamide etc..

Furthermore, it is also possible to include hetero ring type compound, ring-type ammonia base class, nitrogenous ring type compound etc..

As ring-type ammonia base class, such as following chemical formula (3) compound represented can be enumerated.

[changing 2]

(in chemical formula (3), R⁵Indicate that the alkyl of hydrogen or carbon number 1 to 4, e indicate 0 to 3

As chemical formula (3) compound represented, 2-Pyrrolidone, 1-Methyl-2-Pyrrolidone, 1- second can be enumerated Base -2-Pyrrolidone etc..

It is two or more to be able to use a kind of or mixing for these resin dissolubility solvents listed above.In above-mentioned tree In rouge dissolubility solvent, it is preferable that using selected from being made of ring-type ammonia base class, alkoxy amino class, cyclic annular esters and esters It is more than any one of group.In this case, erasibility, adhesion resistance, image quality are further improved.

For the upper limit of the content of resin dissolubility solvent, relative to the all-mass (100 mass %) of printing ink composition, Preferably 25 mass % hereinafter, more preferably 20 mass % hereinafter, further preferably 15 mass % are hereinafter, particularly preferably 10 Quality % or less.In addition, the lower limit of the content for resin dissolubility solvent, the all-mass (100 relative to printing ink composition Quality %), preferably 1 mass % or more, more preferably 3 mass % or more, further preferably 5 mass % or more are especially excellent It is selected as 7 mass % or more.Thus the content of resin dissolubility solvent further improves erasibility and resistance to blocking in the range Reliability.

In addition, in the present embodiment, the content and the first ink group of the resin dissolubility solvent of the second printing ink composition The content for closing the resin dissolubility solvent of object is compared, and preferably more 0.5 mass % or more, 10 mass % are hereinafter, more preferably more 1.0 mass % or more, 8 mass % is hereinafter, further preferably more 3.0 mass % or more, 7.0 mass % or less.By in institute Range is stated, can be improved the low erasibility for occupying the printed article in region especially with the second printing ink composition.In addition, energy The reliability of resistance to blocking when enough ensuring the record of the first more printing ink composition of the content of color material.

1.2.4. water

In the present embodiment, it is preferable that printing ink composition contains water.Water is the main medium of printing ink composition, is The ingredient to disperse is evaporated by heating.Preferably, water is the pure water such as ion exchange water, ultrafiltration water, reverse osmosis water, distilled water Or the water for strongly eliminating ionic impurity as ultrapure water.In addition, utilizing ultraviolet light irradiation or hydrogen peroxide when using When the water that addition etc. is sterilized, in long-term preservation dispersible pigment dispersion and the feelings for the printing ink composition for having used dispersible pigment dispersion Under condition, it is able to suppress the generation of mould, bacterium, is therefore preferred.

It preferably, is 50 mass % or more relative to the content of the water of the all-mass of printing ink composition (100 mass %), More preferably 60 mass % or more, further preferably 70 mass % or more.

1.2.5. organic solvent

Printing ink composition according to the present embodiment can also be containing organic molten other than above-mentioned resin dissolubility solvent Agent.Printing ink composition contains organic solvent, and the drying property for thus spraying printing ink composition on the recording medium is good, can obtain Obtain the excellent image of erasibility.

As the organic solvent for printing ink composition, preferably water-miscible organic solvent.By using water-soluble organic The drying property of solvent, printing ink composition is better, can obtain the excellent image of erasibility.

As the organic solvent other than resin dissolubility solvent, be not particularly limited, for example, can enumerate methanol, ethyl alcohol, The alcohols such as isopropanol；The ketone such as acetone, diacetone alcohol or ketols；The ethers such as tetrahydrofuran, dioxane；Hexylene glycol, ethylene glycol, Diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, butanediol, pentanediol etc. Glycols；The glycol such as glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether it is rudimentary Alkyl ether；Diethanol amine, triethanolamine etc. have the amine of hydroxyl；Glycerol.Improve printing ink composition drying property this On point, wherein it is preferable to use propylene glycol, 1,2- hexylene glycol, 1,3-BDOs etc..

Preferably, relative to the all-mass of printing ink composition (100 mass %) other than resin dissolubility solvent Organic solvent content be 0.5 mass % or more, 30 mass % hereinafter, more preferably 1.0 mass % or more, 25 mass % with Under, particularly preferably 2.0 mass % or more, 20 mass % or less.Preferably, the normal boiling point of organic solvent is at 180 DEG C or more, More preferably 180 DEG C or more 300 DEG C hereinafter, further preferably 200 DEG C or more 270 DEG C hereinafter, particularly preferably 210 DEG C or more 250 DEG C or less.In the content of organic solvent, normal boiling point in the case where above range, the ejection reliability of printing ink composition, Erasibility is more excellent, so ideal.

In addition, sometimes normal boiling point be more than 280 DEG C of sub- alkane polyol system organic solvent absorb ink moisture and The ink near ink gun is thickened, as a result, declines sometimes the ejection stability of ink gun.In addition, the drying property of ink It can decline to a great extent.Therefore, in the present embodiment, it is preferable that the normal boiling point in printing ink composition is more than 280 DEG C of alkylene hydrocarbon The content of the organic solvent of polyalcohol system relative to printing ink composition all-mass (100 mass %) less than 3 mass %, it is more excellent It is selected as less than 2 mass %, more preferably less than 1 mass %, further preferably less than 0.5 mass %, more preferably less than 0.1 mass %.In this case, the drying property for improving the printing ink composition in recording medium is thus particularly suited for low suction The record of the property received recording medium or non-absorbing recording medium, the generation for being capable of forming exudation are able to the excellent image inhibited.This Outside, the viscosity of the printing image of acquisition reduces, and water resistance, erasibility are excellent.

As normal boiling point it is more than the organic solvent of 280 DEG C of sub- alkane polyol system, such as glycerol can be enumerated.Glycerol Hygroscopicity it is higher and boiling point is higher, therefore reason bad as the blocking of ink gun, movement sometimes.In addition, glycerol lacks Weary anti-corrosive properties are easy to make mould, mushroom breeding, and it is therefore preferred to printing ink compositions not to contain glycerol.

1.2.6. surfactant

In the present embodiment, it is preferable that printing ink composition contains surfactant.It is not special as surfactant It does not limit, such as acetylenic glycols system surfactant, fluorine system surfactant and silicone-based surfactant can be enumerated, preferably contain There are at least one of they.

It as acetylenic glycols system surfactant, is not particularly limited, it is preferable that using for example from 2,4,7,9- tetramethyls- The alkylen oxide adducts and 2,4- dimethyl -5- of 5- decine -4,7- glycol and 2,4,7,9- tetramethyl -5- decine -4,7- glycol The alkylen oxide adducts of decine -4- alcohol and 2,4- dimethyl -5- decine -4- alcohol select more than one.As acetylenic glycols system surface The commercially available product of activating agent, is not particularly limited, such as can enumerate the serial (quotient of the E such as 104 series of Olfine, Olfine E1010 The name of an article, Air Prod & Chem's system), Surfynol 465, Surfyno l61, Surfynol DF110D (trade name, day letter Chemical industry Co. Ltd. system) etc..Acetylenic glycols system surfactant also can be used alone, also can be used together two kinds with On.

It as fluorine system surfactant, is not particularly limited, such as fluorinated alkyl sulfonate, perfluoroalkyl carboxylic can be enumerated Hydrochlorate, perfluoralkyl phosphate, perfluoroalkyl ethylene oxide addition product, perfluoroalkyl betain, perfluoroalkyl amine oxide chemical combination Object.As the commercially available product of fluorine system surfactant, be not particularly limited, for example, can enumerate Surflon S144, S145 (more than Trade name, AGC Agc Seimi Chemical Co., Ltd. system)；FC-170C, FC-430, Fluorad-FC4430 (the above trade name, Sumitomo 3M Co. Ltd. system)；FSO, FSO-100, FSN, FSN-100, FS-300 (the above trade name, Dupont corporation)；FT-250, 251 (the above trade name, Neos Co. Ltd. systems).Fluorine system surfactant can be used alone, and also can be used together two kinds More than.

As silicone-based surfactant, be not particularly limited, for example, polysiloxanes based compound can be enumerated, polyethers changes Property organosiloxane etc..It as the commercially available product of silicone-based surfactant, is not particularly limited, specifically, can enumerate BYK-306, BYK-307, BYK-333, BYK-341, BYK-345, BYK-346, BYK-347, BYK-348, BYK-349 (more than Trade name, BYK Additives&Instruments corporation), KF-351A, KF-352A, KF-353, KF-354L, KF- 355A、KF-615A、KF-945、KF-640、KF-642、KF-643、KF-6020、X-22-4515、KF-6011、KF-6012、 KF-6015, KF-6017 (the above trade name, SHIN-ETSU HANTOTAI's Chemical Co., Ltd. system) etc..

Wherein, acetylenic glycols system surfactant can further increase the restorative of the blocking of nozzle.On the other hand, fluorine system Surfactant and silicone-based surfactant have equably spread on the recording medium without generate ink it is deep or light not Even, ink bleed effect is preferred in this regard.Thus, in the present embodiment, it is further preferred that printing ink composition contains There are at least one party in silicone-based surfactant and fluorine system surfactant and acetylenic glycols system surfactant.

All-mass (100 matter for the lower limit of the content of acetylenic glycols system surfactant, relative to printing ink composition Measure %), preferably 0.1 mass % or more, more preferably 0.3 mass % or more, particularly preferably 0.5 mass % or more.It is another Aspect, for the upper limit of content, preferably 5 mass % hereinafter, more preferably 3 mass % hereinafter, particularly preferably 2 mass % with Under.When the content of acetylenic glycols system surfactant is in the range, it is easily obtained the restorative effect for improving the blocking of nozzle Fruit.

The lower limit of fluorine system surfactant and the content of silicone-based surfactant, preferably 0.5 mass % or more, more Preferably 0.8 mass % or more.On the other hand, the upper limit of content, preferably 5 mass % hereinafter, more preferably 3 mass % with Under.When fluorine system surfactant and the content of silicone-based surfactant are in the range, with uniform on the recording medium Deep or light irregular, ink bleed effect of the ground diffusion without generating ink, is preferred in this regard.

1.2.7. others contain ingredient

In the present embodiment, in order to be well maintained its storage stability and from the ejection stability of ink gun, in order to Defoaming agent, dissolution aids, viscosity tune can also be properly added by improving blocking or the deterioration of ink in order to prevent, printing ink composition Save agent, pH adjusting agent, antioxidant, preservative, antifungal agent, corrosion inhibitor, the moisturizer of non-organic solvent and for catching Obtain the various additives such as the chelating agent of metal ion impacted to dispersion.

As pH adjusting agent, such as potassium dihydrogen phosphate, disodium hydrogen phosphate, sodium hydroxide, lithium hydroxide, hydrogen-oxygen can be enumerated Change potassium, ammonia, diethanol amine, triethanolamine, triisopropanolamine, potassium carbonate, sodium carbonate, sodium bicarbonate etc..

As preservative/mould inhibitor, such as sodium benzoate, sodium pentachlorophenol, 2- pyridine mercaptan -1- oxidation can be enumerated Sodium, sodium sorbate, dehydroactic acid sodium, 1,2- benzisothiazole-3-ketone etc..As commercially available product, can enumerate Proxel XL2, Proxel GXL (the above trade name, Avecia corporation), Denicide CSA, NS-500W (the above trade name, Nagase ChemteX Co. Ltd. system) etc..

As antirust agent, such as benzotriazole can be enumerated etc..

As chelating agent, such as ethylenediamine tetra-acetic acid and their salt (ethylenediamine tetra-acetic acid disodium dihydrogen can be enumerated Salt etc.) etc..

As the moisturizer of non-organic solvent, the moisturizer of solid under the room temperature such as trimethylolpropane, sugar can be enumerated.

1.2.8. the preparation method of printing ink composition

In the present embodiment, printing ink composition passes through mixes the ingredient in any order, and as needed into Row filtering etc. removes impurity to obtain.Mixed method as each ingredient is, it is preferable to use to having mechanical agitator, magnetic agitation The container of the agitating device of device etc. the method that successively added material is stirred mixing.It, can be as needed as filter method Carry out centrifugal filtration, filter filtering etc..

1.2.9. the physical property of printing ink composition

In the present embodiment, from the viewpoint for the balance for realizing image quality and the reliability as ink for ink-jet recording It sets out, it is preferable that the surface tension at 20 DEG C of printing ink composition is 18mN/m or more 40mN/m, more preferably 20mN/m or more 35mN/m is hereinafter, further preferably 22mN/m or more 33mN/m or less.Measurement for surface tension, such as be able to use certainly Dynamic surface tension meter CBVP-Z (trade name, interface science Co. Ltd. system of coordinating), is soaked in the environment of 20 DEG C of confirmation with ink Surface tension when platinum sheet measures.

In addition, from the same viewpoint, it is preferable that the viscosity at 20 DEG C of printing ink composition according to the present embodiment For 3mPas or more 10mPas hereinafter, more preferably 3mPas or more 8mPas or less.In addition, the survey for viscosity Amount, such as it is able to use test for viscoelastic machine MCR-300 (trade name, Pysica corporation), to the viscosity in the environment of 20 DEG C It measures.

1.3. reaction solution

Then, reaction solution used in recording method is illustrated.

In addition, in the present embodiment, reaction solution is that the content of color material is 0.2 mass % hereinafter, being not used to note Recording medium coloring above-mentioned aqueous inkjet ink composition, but before or after adhere to water system inkjet ink composition be used for The auxiliary liquid of recording medium attachment.

1.3.1. agglutinant

Preferably, reaction solution used in present embodiment contains the agglutinant for being aggregated the ingredient of printing ink composition.Instead Answering liquid includes agglutinant, thus in aftermentioned printing ink composition attachment process, resin contained by agglutinant and printing ink composition Promptly react.As a result, the dispersity of pigment, resin in printing ink composition is destroyed, pigment, resin agglutination, this is solidifying Collect object and hinder pigment being impregnated with to recording medium, therefore is excellent improving image quality this aspect of record image.

As agglutinant, such as multivalent metal salt, cationic compound (cationic resin, cation can be enumerated Property surfactant etc.), organic acid.These agglutinants also can be used alone, and also can be used together two or more.At these In agglutinant, the excellent this point of reactivity of the resin according to contained by with printing ink composition is, it is preferable to use selected from by polyvalent metal At least one of the group that salt and cationic resin are constituted agglutinant.

As multivalent metal salt, by polyvalent metal ion more than divalent and be incorporated into the yin of these polyvalent metal ions from Son is constituted, and is water-soluble compound.As the concrete example of polyvalent metal ion, Ca can be enumerated²⁺、Cu²⁺、Ni²⁺、Mg² ⁺、Zn²⁺、Ba²⁺Equal bivalent metal ions；Al³⁺、Fe³⁺、Cr³⁺Equal trivalent metal ions.As anion, Cl can be enumerated^-、I^-、 Br^-、SO₄ ^2-、ClO^3-、NO^3-And HCOO^-、CH₃COO^-Deng.In these multivalent metal salts, from the stability of reaction solution, as solidifying , it is preferable to use calcium salt and magnesium salts from the perspective of the reactivity of collection agent.

As organic acid, for example, preferably enumerate phosphoric acid, polyacrylic acid, acetic acid, two alkyd, malonic acid, malic acid, Maleic acid, ascorbic acid, succinic acid, glutaric acid, fumaric acid, citric acid, tartaric acid, lactic acid, sulfonic acid, orthophosphoric acid, pyrrolidones Carboxylic acid, pyrone carboxylic acid, pyrrol-carboxylic acid, furancarboxylic acid, picolinic acid, coumaric acid, thiophene carboxylic acid, niacin or their change Close derivative or their salt etc. of object.Organic acid also can be used alone, and also can be used together two or more.

As cationic resin, for example, can enumerate the polyurethane resin of cationic, cationic olefin resin, The allyl polyimide resin of cationic, polyamines resin, QAS polymer etc..

As the polyurethane resin of cationic, can suitably select using well known resin.As the poly- of cationic Urethane resin is able to use commercially available product, for example, be able to use Hydran CP-7010, CP-7020, CP-7030, CP-7040, CP-7050, CP-7060, CP-7610 (the above trade name, Dainippon Ink. & Chemicals Inc's system), Superflex 600,610,620,630,640,650 (the above trade name, Di-ichi Kogyo Seiyaku Co., Ltd.'s systems), polyaminoester emulsion WBR- 2120C, WBR-2122C (the above trade name, great achievement fine chemistry industry Co. Ltd. system) etc..

The olefin resin of cationic has the alkene such as ethylene, propylene in Tectonic Framework, can suitably select using public affairs The resin known.In addition, the olefin resin of cationic is also possible to the lotion being scattered in the solvent comprising water, organic solvent etc. State.As the olefin resin of cationic, it is able to use commercially available product, such as ArrowBase CB-1200, CD- can be enumerated 1200 (the above trade name, Unitika Co. Ltd. systems) etc..

It as the allyl polyimide resin of cationic, can suitably select using well known resin, such as polyene can be enumerated Propylamin hydrochloride, polyallylamine amidosulphuric acid salt, allylamine hydrochloride/diallylamine hydrochloric acid salt copolymer, allylamine acetate/ Diallylamine acetate copolymers, allylamine hydrochloride/dimethallyl amine hydrochlorate copolymer, allylamine/dimethallyl Amine copolymer object, polydiene propylamin hydrochloride, poly- methyl diallylamine hydrochloride, poly- methyl diallylamine amidosulphuric acid salt, poly- first Base diallylamine acetate, diallyl dimethyl ammoniumchloride, diallylamine acetate/sulfur dioxide copolymer, two allyls Ylmethyl ethyl ammonium sulfovinate/sulfur dioxide copolymer, methyl diallylamine hydrochloride/sulfur dioxide copolymer, diene Diallyidimethylammonium chloride/sulfur dioxide copolymer, diallyldimethylammonium chloride/acrylamide copolymer etc..As this The allyl polyimide resin of the cationic of sample, is able to use commercially available product, for example, be able to use PAA-HCL-01, PAA-HCL-03, PAA-HCL-05、PAA-HCL-3L、PAA-HCL-10L、PAA-H-HCL、PAA-SA、PAA-01、PAA-03、PAA-05、PAA- 08、PAA-15、PAA-15C、PAA-25、PAA-H-10C、PAA-D11-HCL、PAA-D41-HCL、PAA-D19-HCL、PAS- 21CL、PAS-M-1L、PAS-M-1、PAS-22SA、PAS-M-1A、PAS-H-1L、PAS-H-5L、PAS-H-10L、PAS-92、 PAS-92A, PAS-J-81L, PAS-J-81 (the above trade name, Nittobo Medical commercial firm system), HYMO Neo-600, HIMOLOCK Q-101, Q-311, Q-501, Himax SC-505, SC-505 (the above trade name, HYMO Co. Ltd. system) etc..

As cationic surfactant, such as primary, secondary and tertiary amine salt type compound, alkylamine salt, two can be enumerated Alkylamine salt, aliphatic amine salt, zephiran salt, quaternary ammonium salt, alkyl quaternary ammonium salts, Fixanol, sulfonium salt, phosphonium salt, salt, miaow Azoles salt etc..As the concrete example of cationic surfactant, can enumerate the hydrochlorides such as lauryl amine, coco amine, rosin amine, Acetate etc., laurel trimethyl ammonium chloride, cetyl trimethyl ammonium chloride, benzyl tributyl ammonium chloride, salinization zephiran, diformazan Base Ethyl Lauroyl QAE quaternary aminoethyl sulfate, the pungent ammonium sulfovinate of dimethyl ethyl, trimethyl laurel ammonium salt hydrochlorate, cetyl pyrrole Pyridine chloride, cetyl pyridinium bromide, dihydroxyethyl laurylamine amine, chlorination decyl dimethyl benzyl ammonium, chlorination 12 Alkyl dimethyl benzyl ammonium, tetradecyl chloride base dimethyl ammonium, hexadecyl dimethyl ammonium, chlorination octadecyldimethyl Ammonium etc..

In reaction solution 1kg, the concentration of the agglutinant of reaction solution can be 0.03mol/kg or more.In addition, in reaction solution In 1kg, or 0.1mol/kg or more 1.5mol/kg is hereinafter, can also be 0.2mol/kg or more 0.9mol/kg or less. In addition, the all-mass (100 mass %) relative to reaction solution, the content of agglutinant for example can be 0.1 mass % or more 25 Quality % or less, or below 1 mass % or more, 20 mass, or % below 3 mass % or more, 10 mass.

1.3.2. water

Preferably, reaction solution used in present embodiment is using water as the water system of main solvent.The water is to make to react After liquid is attached to recording medium, the ingredient to disperse is evaporated by drying.Preferably, water be ion exchange water, it is ultrafiltration water, anti- The water of ionic impurity is strongly eliminated as the pure water such as infiltration water, distilled water or ultrapure water.In addition, when using by ultraviolet When the water that line irradiation or addition hydrogen peroxide etc. are sterilized, in the case where long-term preservation reaction solution, can prevent mould, The generation of bacterium, is therefore preferred.Relative to the all-mass (100 mass %) of reaction solution, water contained by reaction solution contains Amount can for example be set as 40 mass % or more, preferably 50 mass % or more, more preferably 60 mass % or more, further preferably For 70 mass % or more.

1.3.3. organic solvent

Reaction solution used in present embodiment can also contain organic solvent.By containing organic solvent, can be improved Wetability of the reaction solution to recording medium.As organic solvent, it is able to use and example in above-mentioned aqueous inkjet ink composition The same organic solvent of the organic solvent shown.It for the content of organic solvent, is not particularly limited, the whole relative to reaction solution Quality (100 mass %), such as 10 mass % or more, 80 mass % can be set as hereinafter, preferably 15 mass % or more, 70 matter Measure % or less.

For the normal boiling point of organic solvent, boiled in the standard for the organic solvent that above-mentioned printing ink composition can also contain It, can be independently of printing ink composition or the normal boiling point of the organic solvent contained in the temperature of the preferred range of point.Or Person, it is preferable that the normal boiling point of organic solvent be 180 DEG C or more, more preferably 180 to 300 DEG C, further preferably 190 to 270 DEG C, particularly preferably 200 to 250 DEG C.

In addition, as organic solvent, in the same manner as above-mentioned printing ink composition, normal boiling point is super for reaction solution The content for crossing 280 DEG C of water-miscible organic solvent is preferably 5 mass % hereinafter, more preferably 3 mass % are hereinafter, more preferably 2 Quality % hereinafter, further preferably 1 mass % hereinafter, more preferably 0.5 mass % or less.In the above cases, by It is good in the drying property of reaction solution, therefore in addition to the drying for promptly carrying out reaction solution, the viscosity reduction of the record object of acquisition, Erasibility is excellent.

1.3.4. surfactant

Surfactant can also be added in the reaction solution used in the present embodiment.By adding surfactant, The reduction in surface tension that can make reaction solution can be improved the wetability with recording medium.In surfactant, such as can It is preferable to use acetylenic glycols system surfactants, silicone-based surfactant, fluorine system surfactant.For these surfactants Concrete example, be able to use surface-active same as the surfactant illustrated in aftermentioned aqueous inkjet ink composition Agent.It for the content of surfactant, is not particularly limited, but relative to the all-mass of reaction solution (100 mass %), it can It is set as 0.1 mass % or more, 5 mass % or less.

1.3.5. other ingredients

For reaction solution used in present embodiment, it also can according to need addition pH adjusting agent as described above, prevent Rotten agent/mould inhibitor, antirust agent, chelating agent etc..

1.3.6. the preparation method of reaction solution

Reaction solution used in present embodiment to above-mentioned each ingredient can disperse/mix using method appropriate Conjunction is fabricated.After fully stirring above-mentioned each ingredient, in order to remove the big particle and foreign matter of the reason of becoming blocking And be filtered, so as to obtain goal response liquid.

1.3.7. the physical property of reaction solution

Surface tension in the case where being sprayed by ink gun, at 20 DEG C of the reaction solution used in the present embodiment Preferably 18mN/m or more 40mN/m hereinafter, more preferably 20mN/m or more 35mN/m hereinafter, further preferably 22mN/m with Upper 33mN/m or less.Measurement for surface tension, such as use automatic surface tensometer CBVP-Z (trade name, surface of coordinating Scientific Co. Ltd. system), surface tension when soaking platinum sheet with reaction solution in the environment of confirmation 20 DEG C measures.

In addition, from the same viewpoint, the viscosity at 20 DEG C of reaction solution used in present embodiment is preferably 3mPas or more 10mPas is hereinafter, more preferably 3mPas or more 8mPas or less.In addition, the measurement for viscosity, Such as it is able to use test for viscoelastic machine MCR-300 (trade name, Pysica corporation), the viscosity in the environment of 20 DEG C is carried out Measurement.

1.4. recording medium

Above-mentioned printing ink composition has ink setting, for ink absorption, ink nonabsorbable or low absorption In the record of the recording medium of property, the excellent image of image quality, erasibility can be obtained.Wherein, above-mentioned printing ink composition with it is upper The reaction solution stated is used together, thus, it is possible to the recording medium relative to ink nonabsorbable or low absorption use well it is upper The printing ink composition stated.

As the recording medium of ink absorption, such as the higher cotton of ink absorption, thin,tough silk, polyester, poly- ammonia can be enumerated The plain papers such as the clothes such as ester, nylon, plain paper, ink jet special paper, the good quality paper of moderate absorbability, recycled writing paper are duplicated With paper, the ink jet special paper for being provided with the ink receiving layer with ink absorbability etc..

As the recording medium of ink nonabsorbable, such as it can enumerate for ink-jet record and surface treatment is not carried out It is coated with the recording medium of plastics on the substrates such as the plastic foil, paper of (that is, not formed ink absorbing layer), is bonded with the note of plastic foil Recording medium etc..As plastics said here, polyvinyl chloride can be enumerated, polyethylene terephthalate, polycarbonate, gathered Styrene, polyurethane, polyethylene, polypropylene etc..

As the recording medium of ink low absorption, it can enumerate and the note for receiving the coat of ink is set on surface Recording medium can enumerate the printings such as art paper, coating paper, dumb light paper for example, being the recording medium of paper as substrate, Substrate is the recording medium of plastic foil, can enumerate polyvinyl chloride, polyethylene terephthalate, polycarbonate, polyphenyl second The surface of alkene, polyurethane, polyethylene, polypropylene etc. is coated with the recording medium of hydrophilic polymer, coats together with adhesive There is the recording medium of the particles such as silica, titanium.These recording mediums are also possible to transparent recording medium.

Wherein, " recording medium of ink nonabsorbable or low absorption " expression " Bristol in this specification (Bristow) Fa Zhongcong comes into contact with 30msec^1/2Until water uptake be 10mL/m²Recording medium below ".The cloth Li Situofa is the method the most universal as the measurement method of the liquid absorption amount in the short time, is also assisted by Japanese pulp technology Meeting (JAPAN TAPPI) uses.The details of test method describe the mark in " JAPAN TAPPI paper pulp test method version in 2000 " In quasi- No.51 " paper and cardboard-liquid-absorbent test method-Bristol method ".

Additionally it is possible to which being preferably used for being embossed the surfaces such as medium has indent and convex ink nonabsorbable or low absorption Recording medium.

2. recording method

Recording method according to the present embodiment is the record carried out using above-mentioned ink group according to the present embodiment Method, which is characterized in that have: the process for adhering to reaction solution to recording medium；Make the first printing ink composition to recording medium The process of attachment；And the process for adhering to the second printing ink composition to recording medium.In the following, for note according to the present embodiment Recording method is enumerated and is illustrated using the example that above-mentioned ink-jet recording apparatus is recorded.

2.1. reaction solution adheres to process

It is the work for adhering to the above-mentioned reaction solution reacted with printing ink composition to recording medium that reaction solution, which adheres to process, Sequence.By adhering to reaction solution to recording medium, erasibility, the image quality of the printing image of acquisition can be improved.

Reaction solution adheres to process both can be laggard before the attachment of printing ink composition or in the attachment of printing ink composition Row, in addition it is also possible to which the attachment with printing ink composition carries out simultaneously.The feelings for adhering to reaction solution before the attachment of printing ink composition Under condition, it is preferable that adhere to process using pre-heater 7 shown in FIG. 1 or carrying out reaction solution before reaction solution adheres to process When recording medium M is heated using IR heater 3 shown in FIG. 1 or laminate heater 4.By being attached to reaction solution On the recording medium M being heated, the reaction solution being ejected on recording medium M is easy to be coated with diffusion, Neng Goujun on recording medium M Even coating reaction solution.Therefore, the ink adhered in aftermentioned printing ink composition attachment process is fully reacted with reaction solution, can Obtain excellent image quality.Further, since reaction solution is equably coated on recording medium M, therefore can reduce coating weight, it can Prevent the erasibility decline of the image obtained.

Wherein, when the surface temperature of recording medium M when enabling reaction solution to adhere to is independently of the attachment of aftermentioned ink is made The temperature of preferred range of surface temperature (primary heating temperature) of recording medium M set.For example, keeping reaction solution attached When recording medium M surface temperature be preferably 45 DEG C hereinafter, more preferably 40 DEG C hereinafter, further preferably 38 DEG C with Under.In addition, the lower limit value of the surface temperature of recording medium M when adhering to reaction solution is preferably 25 DEG C or more, more preferably 30 DEG C or more.The surface temperature of recording medium M when adhering to reaction solution, can be by reaction solution in the case where the range It is equably coated on recording medium M, can be improved erasibility, image quality.Furthermore it is possible to inhibit influence of the heat to ink gun 2.

In addition, the attachment of reaction solution can be by the progress of gushing out implemented by ink gun 2, for side in addition to this Method, such as method, the method for spraying reaction solution etc. of the coating reaction solution such as can enumerate roll coater.

2.2. printing ink composition adheres to process

Printing ink composition attachment process is the process for spraying above-mentioned printing ink composition from ink gun 2 and adhering to it, benefit With the process, the image being made of printing ink composition is formed on the surface of recording medium M.

In the present embodiment, " image " indicates the recording figure forming formed by group, also comprising text printing, full version figure Picture.In addition, " full version image " refers to, for the whole of the pixel as smallest record unit area limited by log resolution Pixel record point, usually expression should be the surfaces that recording medium is not seen after the record area of recording medium is covered by ink The picture pattern of image.

Wherein, in the present embodiment, printing ink composition attachment process includes to make the first printing ink composition to recording medium The process of attachment and the process for adhering to the second printing ink composition to recording medium, wherein make the first printing ink composition to record The process of medium attachment and the process for adhering to the second printing ink composition to recording medium can both carry out simultaneously, can also be different Shi Jinhang.

Maximum adhesion amount for the printing ink composition of the per unit area of recording medium M is preferably 5mg/inch²More than, More preferably 7mg/inch²More than, further preferably 10mg/inch²More than.For the oil of the per unit area of recording medium The upper limit of the adhesion amount of ink composition, is not particularly limited, such as preferably 20mg/inch²Hereinafter, preferably 18mg/inch² Hereinafter, being particularly preferably 16mg/inch²Below.In addition, the maximum adhesion amount of the printing ink composition is the first ink combination Total adhesion amount of object and the adhesion amount of the second printing ink composition.

Printing ink composition attachment process can also have printing ink composition adhere to process before or with printing ink composition it is attached Process simultaneously, the heating process that recording medium M is heated using IR heater 3, laminate heater 4, it is preferable that right Implement printing ink composition by the recording medium M that heating process is heated and adheres to process.Thereby, it is possible to make on recording medium M Ink is promptly dried, and exudation is inhibited.Furthermore it is possible to form erasibility, adhesion resistance and the excellent image of image quality, and pass through Using above-mentioned ink, it is capable of providing the ink jet recording method for spraying excellent in stability.

The upper limit of the surface temperature (primary heating temperature) of recording medium M when adhering to ink be preferably 45 DEG C hereinafter, More preferably 40 DEG C hereinafter, further preferably 38 DEG C or less.The surface temperature of recording medium when adhering to ink is described Range can prevent the blocking of ink gun 2, nozzle thus, it is possible to inhibit influence of the heat to ink gun 2.In addition, ink-jet record When the lower limit of surface temperature of recording medium M be preferably 25 DEG C or more, more preferably 28 DEG C or more, further preferably 30 DEG C More than, particularly preferably 32 DEG C or more.Ink-jet record when recording medium M surface temperature in the range, thus, it is possible to It is enough to make ink promptly dry on recording medium M and fix in advance, inhibit exudation, it is excellent to be capable of forming erasibility, image quality Image.

2.3. reheating process

Recording method according to the present embodiment can also have after above-mentioned printing ink composition adheres to process and utilize Fig. 1 Shown in solidify the reheating process that heater 5 heats the recording medium M for being attached with printing ink composition.Remember as a result, Fixing resin etc. contained by printing ink composition on recording medium M dissolves and forms ink film, secured in the recording medium M ink film that oils Ground is fixed (bonding), so that film forming is excellent, the image of the excellent high image quality of erasibility can be obtained with the short time.

The upper limit for solidifying the surface temperature of the recording medium M of the realization of heater 5 is preferably 120 DEG C hereinafter, more preferably 110 DEG C hereinafter, more preferably 100 DEG C or less.In addition, the lower limit of the surface temperature of recording medium M is preferably 60 DEG C or more, it is more excellent It is selected as 70 DEG C or more, more preferably 80 DEG C or more.For temperature in the range, thus, it is possible to the figure of high image quality is obtained with the short time Picture.

In addition, can also have using cooling fan 6 shown in FIG. 1 after reheating process on recording medium M Printing ink composition carries out cooling process.

2.4. other processes

Ink jet recording method according to the present embodiment can also have: using in addition to being recorded for spraying ink Means other than pressure generation means, that is to say, that using not ink gun 2 have in order to record and spray the mechanism of ink Other mechanisms, discharge printing ink composition, reaction solution cleaning process.

As ink gun 2 have in order to record and spray the mechanism of ink, can enumerate and be installed on pressure chamber 21 and right Piezoelectric element, the heating element of ink imparting pressure.The cleaning process may be set to be to assign ink gun 2 from outside and press Power and from nozzle be discharged printing ink composition, the process of reaction solution.By having the process, even if there are the inner walls of ink gun 2 In the case where a possibility that being deposited with resin, it is also able to suppress the generation of above situation, ejection stability can be made more excellent.

In addition, can enumerate imparting as above-mentioned other mechanisms and attract (negative pressure), assigned just from the upstream of ink gun Pressure etc. assigns the mechanism of pressure.(flushing) is discharged not by the ink that the function of ink gun itself is implemented in this.That is, It is not to be discharged using the function of ink is sprayed from ink gun when being recorded.

As shown above, in ink group and recording method according to the present embodiment, the content of color material is less than first The content of the fixing resin of second printing ink composition of printing ink composition is set as more than the first printing ink composition, and in recording medium The content of the resin dissolubility solvent of upper dissolving resin is also more than the first printing ink composition, and thus, it is possible to improve to use the second ink The low erasibility for occupying region of composition.In addition, temperature raising when without making record can shape by using reaction solution At image quality, so can ensure the ejection stability of head, in the recording method using deep or light ink, being capable of providing can be taken into account The ink group of erasibility and the reliability of resistance to blocking.

3. embodiment

In the following, embodiments of the present invention are further concretely demonstrated using Examples and Comparative Examples, but this reality The mode of applying is not limited to these embodiments.

3.1. the preparation of ink and reaction solution

Each ingredient be mixed and is filtered using the molecular filter in 5 μm of aperture to become the mixing that table 1 is recorded Ratio obtains reaction solution 1 to 4, dense ink 1 to 6 and light ink 1 to 8.Numerical value in table 1 all indicates that quality %, water are added to So that the all-mass of ink becomes 100 mass %.In addition, showing for pigment and resin and having carried out solid component conversion Value.

About SP value, for solvent, using the calculating SP value (δ) of Hildebrand shown in Formulas I, for resin, Know that the resin solid content concentration that resin is added in liquid is added in the solvent of SP value becomes 0.5 mass %, visual confirmation resin Dispersion stabilization, using the lower value of dispersible SP value as resin SP value.

[numerical expression 2]

Details as Follows for substance recorded in table 1.

Multivalent metal salt: magnesium sulfate/7 hydrates

Cationic resin: Cation Master PD-7 (trade name, Yokkaichi synthesize Co. Ltd. system)

Organic acid: malonic acid

Green pigment: C.I. pigment blue 15: 3 (PB15:3)

<resin>

Resin A (SP value: 17, reactive: low): Elitel KT8701 (trade name, Unitica Co. Ltd. system)

Resin B (SP value: 20, reactive: low): Epocros K-2030E (trade name, Nippon Catalyst K. K. System)

Resin C (SP value: 17, reactive: high): AQUACER539 (trade name, Japanese BYK Chemie Co., Ltd. System)

Silicone type surface active agent: BYK348 (trade name, Japanese BYK Chemie Co. Ltd. system)

3.2. the reactive evaluation of resin

For above-mentioned Resin A, B, C, in the environment of 25 DEG C, confirmation will make 1 mass % of solid component concentration points with 1:1 The average grain diameter (D50) when the magnesium sulfate reaction solution for the resin liquid and 0.3M that water is formed stirs 1 minute is dissipated, according to following Benchmark evaluates the reactivity of resin.

(evaluation criteria)

Reactivity is low: the increase of average grain diameter is less than 5 times.

Reactive high: the increase of average grain diameter is at 5 times or more.

3.3. the evaluation of ink group and recording method

Then, the reaction solution and deep or light ink recorded using table 1 carry out evaluation test.

3.3.1. image is formed

Prepare ink-jet printer (trade name " PX-G930 ", Seiko Epson Corp's system) transformation apparatus, it can be to pressing plate Heater carry out temperature adjusting.As recording medium, using inside and outside signature with polychloroethylene film (trade name " IJ180-10 ", 3MJapan Co. Ltd. system).

Firstly, to the head of ink-jet printer filling reaction solution, dense ink and light ink, to pour 10 matter of fluence compared to ink-jet Measure the amount ink-jet application reaction solution of %.Then, 12mg/inch is become with ink adhesion quantity²Adhesion amount (dense ink 6mg/ inch², light ink 6mg/inch²) amount, the deep or light ink jet inks for being filled in head are coated on reaction solution attachment surface, are made deep or light Mix full version image.So that laminate heater is worked in ink-jet application, the surface temperature of recording medium is adjusted to table 2,3 and is recorded Primary heating temperature.After record, recording medium is discharged from printer and is what table 2,3 was recorded in the surface temperature of recording medium It is dried at a temperature of reheating temperature.The visually image that judgement obtains, is evaluated according to following benchmark.

(evaluation criteria)

A: it is detained in full version face without deep or light irregular, recess ink.

B: without deep or light irregular in full version face, but the ink of recess slightly is detained.

C: there is deep or light irregular, recess ink delay in full version face.

3.3.2. the evaluation of erasibility

Reaction solution, dense ink and light ink are filled in the head of ink-jet printer, to pour 10 mass % of fluence compared to ink-jet Amount ink-jet application reaction solution.Then, 6mg/inch is become with ink adhesion quantity²Adhesion amount (dense ink 3mg/inch², light oil Black 3mg/inch²) the deep or light ink jet inks for being filled in head are coated on reaction solution attachment surface by amount, deep or light mixed image is made.? When ink-jet application, laminate heater is made to work, the surface temperature of recording medium is adjusted to the primary heating temperature of the record of table 2,3 Degree.After record, recording medium is discharged from printer and is the reheating temperature that table 2,3 is recorded in the surface temperature of recording medium At a temperature of it is dry.

For the printed article of acquisition, erasibility/moisture-proof frictional property: vibration shape friction fastness test machine AB-301 is used The evaluation of (trade name, TESTER industry companies system) progress erasibility.Specifically, using byssus is equipped with (according to JIS L 0803) friction member applies load 500g reciprocating friction 10 times and records the surface for having the recording medium of image.Also, visually observation The removing situation of the image (film) on the surface of recording medium, is evaluated according to following benchmark.

(evaluation criteria)

When A: load 500g friction 10 times, removing is not generated.

When B: load 500g friction 10 times, 10% removing is generated less than relative to evaluation area.

When C: load 500g friction 10 times, 10% or more removing is generated relative to evaluation area.

3.3.3. the restorative evaluation blocked

In the recording medium of A4 size, 50 image recordings are carried out continuously with the condition of above-mentioned 3.3.1., according to following Benchmark evaluation record after nozzle rows nozzle state.

(evaluation criteria)

A: without generating nozzle missing/bending printing 50.

B: when printing 50 is opened, nozzle bending is generated.

C: when printing 50 is opened, nozzle missing is generated.

3.4. evaluation result

The result of evaluation test is as shown in the lower section of table 2,3.In addition, in the evaluation of 3 evaluation tests, evaluation are as follows: A: Very good, B: good (purposes restriction), C: unusable.

Even if in any embodiment, good quanlity, the result of the reliability of erasibility and resistance to blocking is also good.Especially Be, in the embodiment 1 of table 2, even if in the image formed using dense ink, either one in light ink, image quality, erasibility and The reliability of resistance to blocking is all excellent.

Specifically, embodiment 1 is compared with Example 2 compared with due to without containing the alkylene for as normal boiling point being more than 280 DEG C The glycerol of the organic solvent of hydrocarbon polyalcohol system, therefore erasibility is excellent compared with Example 2.In addition, in embodiment 1, with reality Apply example 3 compare be fixed resin SP value it is lower, and resin dissolubility solvent SP value difference it is smaller, therefore in recording medium The dissolubility for being fixed resin is higher, and erasibility is excellent compared with Example 3.Moreover, the thin oil compared with Example 4 of embodiment 1 The content of the fixing resin of ink is appropriate, therefore resistance to blocking compared with Example 4 is excellent in reliability.In addition, embodiment 1 and implementation Example 5 is also appropriate compared to the content of the resin dissolubility solvent of thin ink, therefore the reliability of resistance to blocking is still excellent.Also, Embodiment 1 is lower compared with the reactivity of resin compared with Example 6, therefore erasibility is excellent compared with Example 6.

In addition, temperature when for record and after record, in embodiment 1, when being recorded compared with the embodiment 7 of table 3 Temperature it is lower, therefore resistance to blocking compared with Example 7 is excellent in reliability.In addition, in embodiment 1, compared with Example 8 It is higher compared with reheating temperature, therefore fixing resin sufficiently dissolves and is implemented as membranization on the recording medium, compared with Example 8 Erasibility is also excellent.

Is compared by organic acid, has been used as agglutinant more according to embodiment 1,9,10 for agglutinant contained by reaction solution The embodiment of valence metal salt or cationic resin is excellent in terms of image is formed with erasibility.

Relative to above-described embodiment, in comparative example 1, the content of the fixing resin of light ink is fewer than dense ink, especially exists In the image formed using light ink, in addition to being formed with deep or light irregular, recess ink in full version face and being detained, especially using The region erasibility of light ink is deteriorated.In addition, the content of the resin dissolubility solvent of dense ink is more than light in comparative example 2 Ink, resin dissolves and generates blocking in the nozzle of dense ink side.In comparative example 3, due to not using reaction solution, In the image that either one is formed in using dense ink, light ink, image quality is deteriorated.

As described above, in any embodiment, being recorded using reaction solution, the content of the fixing resin of light ink is more than The content of the fixing resin of dense ink, the content of the resin dissolubility solvent of light ink are more than the resin dissolubility solvent of dense ink Content, the result of thus good quanlity, the reliability of erasibility and resistance to blocking is also good.

The present invention is not limited to above-mentioned embodiments, can there is various modifications.For example, the present invention includes and embodiment party Substantially the same structure of the composition illustrated in formula is (for example, function, method and the identical structure of result or purpose and effect phase Same structure).In addition, the present invention includes that the composition of the nonessential part of the composition illustrated in embodiment is substituted.In addition, The present invention includes the composition for the identical function and effect of composition that can be played with illustrate in embodiment or reaches identical purpose Composition.In addition, the present invention includes that attached the composition of well-known technique to the composition illustrated in embodiment.

Claims

1. a kind of ink group, which is characterized in that record together with the reaction solution that the ingredient reaction with printing ink composition is aggregated Medium attachment, the ink group have:

First printing ink composition, it includes color material, fixing resin and resin dissolubility solvents；And

Second printing ink composition, it includes color material, fixing resin and resin dissolubility solvent, second printing ink composition and institutes The first printing ink composition identical colour system ink each other is stated,

According to quality criteria, the content of the color material of second printing ink composition contains than the color material of first printing ink composition Amount is few,

According to quality criteria, second printing ink composition fixing resin content than first printing ink composition fixing The content of resin is more,

According to quality criteria, the content of the resin dissolubility solvent of second printing ink composition is than first printing ink composition Resin dissolubility solvent content it is more.

2. ink group according to claim 1, which is characterized in that

The fixing resin that second printing ink composition is included includes: in the environment of 25 DEG C, with the mass ratio of 1:1 by 0.3M When magnesium sulfate solution and resin liquid stir 1 minute, resin of the variation less than 5 times of average grain diameter, the resin liquid is will to set 1 mass % of rouge is scattered in obtained by water.

3. ink group according to claim 1 or 2, which is characterized in that

The content phase of the fixing resin of the content and first printing ink composition of the fixing resin of second printing ink composition Than more 0.5 mass % or more, 5 mass % or less.

4. ink group according to any one of claim 1 to 3, which is characterized in that

The content of the resin dissolubility solvent of second printing ink composition and the resin dissolubility solvent of first printing ink composition Content compare more 0.5 mass % or more, 10 mass % or less.

5. ink group according to any one of claim 1 to 4, which is characterized in that

The content of the resin dissolubility solvent of second printing ink composition is 20 mass % or less.

6. ink group according to any one of claim 1 to 5, which is characterized in that

The normal boiling point of first printing ink composition and second printing ink composition is more than 280 DEG C of sub- alkane polyol The content of the organic solvent of system is respectively smaller than 1 mass %.

7. ink group according to any one of claim 1 to 6, which is characterized in that

The difference of resin dissolubility solvent and fixing resin comprising SP value that second printing ink composition is included is each other within 5 Resin dissolubility solvent and fixing resin.

8. a kind of recording method, which is characterized in that carried out using ink group described in any one of any one of claims 1 to 77, the note Recording method has:

The process for adhering to the reaction solution to recording medium；The work for adhering to first printing ink composition to recording medium Sequence；And the process for adhering to second printing ink composition to recording medium.

9. recording method according to claim 8, which is characterized in that

Process from first printing ink composition to recording medium that adhere to and make second printing ink composition to recording medium The surface temperature of recording medium in the process of attachment be 45 DEG C hereinafter,

In the reheating process heated after each process to recording medium, the surface temperature of recording medium be 70 DEG C with On.

10. recording method according to claim 8 or claim 9, which is characterized in that

Include any number of agglutination for being included as the reaction solution in multivalent metal salt, cationic resin or organic acid Agent.